Attrition resistant molecular sieve catalyst

ABSTRACT

This invention provides a process for making an attrition resistant molecular sieve catalyst composition. The formation of highly attrition resistant catalyst particles is accomplished by initially mixing together catalyst components to form a slurry at a relatively low viscosity and high solids content. Preferably, a slurry having characteristics of high solids content and low viscosity is achieved using a rotor-stator mixer. Once the desired slurry characteristics are obtained, the slurry is dried, preferably by spray drying and calcining, to form a highly attrition resistant catalyst.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to Provisional application filed onNov. 2, 2005, U.S. Ser. No. 60/732,546.

FIELD OF THE INVENTION

This invention relates to methods of making and using molecular sievecatalyst. In particular, the invention relates to methods of making andusing metalloaluminophosphate molecular sieve catalyst that is highlyattrition resistant.

BACKGROUND OF THE INVENTION

A desirable characteristic for certain molecular sieve catalysts,regardless of the process of use, is that the finished or formulatedcatalyst be attrition resistant. Attrition resistance can refer tohardness as well as ability to absorb shock, since the catalyst willtypically have to endure severe stress in commercial scale processes.

For example, WO 99/21651 describes a method for making molecular sievecatalyst that is considered relatively hard. The method includes thesteps of mixing together a molecular sieve and an alumina sol, thealumina sol being made in solution and maintained at a pH of 2 to 10.The mixture is then spray dried and calcined. The calcined product isreported to be relatively hard.

U.S. Pat. No. 6,153,552 describes another method for making molecularsieve catalyst. The catalyst is made by mixing together a siliconcontaining oxide sol as a binder material and a molecular sievematerial. The pH of the mixture is adjusted prior to spray drying.Following spray drying, the catalyst material is calcined to form afinished catalyst product, which is reported to be relatively hard.

Attrition resistance continues to be a desirable characteristic inmolecular sieve catalysts. As new process systems are developed, theability of the catalyst to endure the stress of the process system isparticularly important so as to increase the effective life of thecatalyst in the reaction process. If the catalyst is not properlyattrition resistant, it is likely to break apart at an early stage,meaning that the catalyst could only be effectively used for arelatively short period of time. Therefore, obtaining molecular sievecatalysts that have a high degree of attrition resistance are stillsought. Methods that are particularly effective at making highlyattrition resistant molecular sieve catalysts at commercial scale are inparticularly high demand.

SUMMARY OF THE INVENTION

This invention provides methods for making and using highly attritionresistant molecular sieve catalyst. The methods are particularlyeffective at commercial scale manufacture. In general, the methodsinclude making a slurry of catalyst components at relatively high solidscontent and low viscosity using a rotor-stator mixer, then drying theslurry to form the finished catalyst.

According to one aspect of the invention, there is provided a method ofmaking an attrition resistant molecular sieve catalyst composition. Themethod comprises mixing together molecular sieve crystals, clay, binderand liquid with a rotor-stator mixer to form a slurry having a solidscontent of at least 40 wt %, based on total weight of the slurry.

In one embodiment, the rotor and stator have a gap distance of notgreater than 0.3 mm. Preferably, the stator has at least one holedefining an opening of not greater than 9 mm².

In another embodiment, slurry mixing is progressed until the slurryviscosity decreases to a noticeable extent. Preferably, the mixing isprogressed until the viscosity is decreased by at least about 10%, morepreferably by at least 15%, and most preferably by at least 10%.

In one embodiment, the molecular sieve crystals, clay, binder and liquidare mixed to form a slurry having a viscosity of not greater than 10,000cP. After thorough mixing, the slurry product is preferably dried toproduce a dried molecular sieve catalyst composition having an attritionrate index of not greater than 2 wt %/hr.

The dried catalyst composition can be used in any variety of processes.One preferred process is for use in the manufacture of olefins, whereinthe dried molecular sieve catalyst is contacted with oxygenate to formolefin product.

In one embodiment, the stator includes at least one polygonal shapedhole. Prefearbly, the at least one polygonal shaped hole has at leastone angle not greater than 90 degrees. More preferably, the at least onepolygonal shaped hole is a rectangle. In a particular embodiment, the atleast one polygonal shaped hole is a square.

The rotor is rotated at a speed sufficient to provide thorough mixing,preferably at a speed where viscosity of the slurry decreases as theslurry components are mixed. In one embodiment, the rotor is rotated ata tip speed of at least 5 m/sec.

The slurry can be dried by a combination of spray drying and calcining.Preferably, the slurry is dried using a spray dryer and the spray driedproduct is calcined.

In one embodiment, the molecular sieve particles aremetalloaluminophosphate molecular sieve crystals.

DETAILED DESCRIPTION OF THE INVENTION

I. Forming a High Solids, Low Viscosity Slurry

This invention provides a process for making an attrition resistantmolecular sieve catalyst composition. The process includes mixingtogether the catalyst components with liquid to form a slurry, anddrying the slurry to form the catalyst.

The formation of highly attrition resistant catalyst particles isaccomplished by initially making a slurry having a relatively highsolids content. In particular, the slurry is mixed to a relatively lowviscosity, taking into consideration the high solids content. Then theslurry is dried, preferably by spray drying and calcining, to form ahighly attrition resistant catalyst.

According to this invention, attrition resistant refers to the abilityto resist breaking apart as a result of physical impact. Since molecularsieve catalysts are often used in fluidized-bed reaction systems orriser-type reaction systems, the ability of such catalysts to avoidphysical damage within the reaction systems is important. Attritionresistance, however, does not necessarily mean that the catalyst ishard, although hardness is a desirable characteristic. Attritionresistance can also be obtained through such characteristics as acatalyst's ability to absorb shock from impact as the catalyst iscirculated through the reaction system. In some sense, the ability ofthe catalyst to absorb shock is similar to the ability of a ball tobounce off a hard surface with deforming the ball. The catalyst formedby the process of this invention is particularly attrition resistant.

II. Method of Mixing Slurry Components

This invention includes a method or step of mixing together catalystcomponents and liquid to form a slurry having a high solids content anda relatively low viscosity. This mixing method or step is successfullyaccomplished using a desired mixer having certain appropriate settings.

As is understood by those of skill in the art, selecting an efficientmixer for a particular task can be a major component to successfulprocessing, and processing technique has come to play an increasinglyvital role in maintaining competitive advantage and profit margins.Therefore, choosing the right mixer for a particular mixing process canbe a somewhat complex task, and huge variations in applications have ledto a particularly diverse array of mixing equipment.

In the manufacture of molecular sieve catalysts, slurries are made ofmolecular sieve crystals and liquid (e.g., water), and possibly numerousother ingredients depending upon the characteristics desired of thefinished catalyst product. These slurries are then dried to form a finalor formulated molecular sieve product. The slurry that is ultimatelydried to form the final molecular sieve product can vary widely incharacteristics.

According to this invention, a slurry having characteristics of highsolids content and low viscosity is achieved using a rotor-stator mixer.Rotor-stator mixers generally include a high-speed centrifugal-typerotor mounted within a stator. Typically, the stator is held in place byframe arms.

During operation, high-speed rotor revolution creates a suction thatdraws a mixture of liquid and solid materials into the center of theworkhead assembly, where the mixture is subjected to a shear force, orit is assisted by external means (e.g., by using a feed pump).Centrifugal force then drives the materials to the periphery of theworkhead, where the mixture encounters milling action in the clearancebetween the rotor blade tips and the stator inner wall. Hydraulic shearfollows as the materials are forced out through the openings in thestator and are projected radially back into the body of the mixture.

The size and shape of openings in the stator (often referred to as thestator geometry) and the clearance between the rotor blade tips and thestator inner wall (typically referred to as gap distance) determine theflow pattern and the machine's shear rates. For example, a stator withround holes gives a type of mixing action that is particularly suitedfor disintegrating solids and preparing gels, suspensions, andsolutions. Slotted holes produce a somewhat scissor-like shearing actionthat is particularly appropriate for disintegrating elastic or fibrousmaterials. Fine screens are typically used where a high degree ofparticle- or globule-size reduction is desired and for preparation offine colloidal suspensions and emulsions.

In this invention the rotor and stator are arranged so that very highsolids slurry compositions can be prepared at relatively lowviscosities. An advantage in making high solids, low viscosity slurriesis that in the preparation of molecular sieve catalyst compositions, adried product of this type of slurry can be highly attrition resistant.In one embodiment of this invention, the rotor and stator have a gapdistance of not greater than 0.3 mm, preferably 0.28 mm. In anotherembodiment, the rotor and stator have a gap distance of not greater than0.25 mm, more preferably not greater than 0.2 mm, and most preferablynot greater than 0.15 mm.

In another embodiment of the invention, the stator has at least 4 holesper square inch of surface area. Preferably, the stator has at least 6holes per square inch of surface area, more preferably at least 8 holesper square inch of surface area.

In another embodiment, each stator hole defines an opening of notgreater than 9 mm². Preferably, each stator hole defines an opening ofnot greater than 7.5 mm², more preferably not greater than 7 mm², andmost preferably not greater than 6.5 mm².

The stator holes can be of any shape suitable to making the desiredcatalyst slurry mixture. The holes can be of the same shape or varied.Non-limiting examples of various shapes can include holes that areround, oval, rectangular, pyramidal, polygonal, or any combinationthereof. Preferably, a majority of the holes are a shape other thanround. Polygonal shapes are particularly preferred, with polygonal beingdefined as a closed plane figure bounded by straight lines. Morepreferably, the stator includes at least one polygonal shaped hole, thepolygon having at least one angle not greater than 90 degrees.Rectangular, particularly square, shapes are most preferred.

Mixing can be carried out using batch (“in-tank” type) mixing units orcontinuous (“in-line” type) mixing units, and the processes can becarried out quite effectively at commercial scale. In-tank mixers havingthe desired characteristics can function to form a slurry in a tank offrom 1 gallon to 30,000 gallons. In-line mixers are preferred in thatthey can be used in a continuous manufacturing process. Such mixers areparticularly suited for processing flow rates of slurry components of atleast 100 liters per hour. Preferred rates of processing are at least200 liters per hour. Mixers that can process slurry at rates of at least400 liters per hour or at least 800 liters per hour can also be used.

The slurry is mixed at a relatively high viscosity and as the mixing isprogressed, the viscosity preferably decreases. In one embodiment, theslurry is mixed until the viscosity is decreased by at least about 10%,preferably by at least 15%, and more preferably by at least 20%.

The slurry product should not be too viscous as formation of highlyattrition resistant catalyst particles can be adversely affected. In oneembodiment, the slurry is mixed to form a slurry product having aviscosity of not greater than 10,000 cP. Preferably, the slurry producthas a viscosity of not greater than 9000 cP, more preferably not greaterthan 8000 cP.

The slurry product should also be sufficiently viscous as formation ofcatalyst particles during spray drying can be difficult. In oneembodiment, the slurry product has a viscosity of at least 500 cP.Preferably, the slurry product has a viscosity of at least 600 cP, morepreferably at least 700 cP.

The slurry can be mixed using a batch type mixing process or using anin-line mixing process. In-line mixing can be accomplished using norecyle or using recyle. In a preferred embodiment, recycling is used.Preferably, the molecular sieve crystals, clay, binder and liquid aremixed with an in-line rotor-stator mixer applying recycle at a number ofpasses of at least 1, more preferably at least 2, and most preferably atleast 3.

The rotor should be rotated at a tip speed sufficient to thoroughly mixthe slurry of high solids content and to ultimately provide a slurryhaving the desired low viscosity. Tip speed (ν, in m/sec) is defined asν=ω*φ*π* 2.54/100/60, where ω is rotation speed in rpm and φ is rotordiameter in inches. In one embodiment, the rotor is rotated at a tipspeed of at least 5 m/sec. Preferably, the rotor is rotated at a speedof at least 6 m/sec, more preferably at least 6.5 m/sec, and mostpreferably at least 7 m/sec.

III. Slurry Components

A. Overall Composition

The catalyst of this invention is a molecular sieve catalystcomposition, which comprises molecular sieve crystals, clay, and binder.Such a combination is generally referred to as a formulated catalyst. Inone aspect, the formulated catalyst composition is characterized bybeing highly resistant to attrition.

B. Molecular Sieve Crystal Component

The molecular sieve particles used to make the formulated catalystinclude any of a variety of molecular sieve components. The componentsinclude zeolites or non-zeolites, preferably non-zeolites. In oneembodiment, the molecular sieves are small pore non-zeolite molecularsieves having an average pore size of less than about 5 angstroms,preferably an average pore size ranging from about 3 to 5 angstroms,more preferably from 3.5 to 4.2 angstroms. These pore sizes are typicalof molecular sieves having 8 membered rings.

Conventional crystalline aluminosilicate zeolites having catalyticactivity are desirable molecular sieves that can be used in making thecatalyst of this invention. Non-limiting examples of zeolites which canbe employed in the practice of this invention, include both natural andsynthetic zeolites. These zeolites include zeolites of the structuraltypes included in the Atlas of Zeolite Framework Types, edited by Ch.Baerlocher, W. M. Meier, D. H. Olson, Fifth Revised edition, Elsevier,Amsterdam, 2001.

Additional examples of molecular sieve particles used to make formulatedmolecular sieve catalyst according to this invention include zeolite aswell as non-zeolite molecular sieves, and are of the large, medium, orsmall pore type. Non-limiting examples of these molecular sieves are thesmall pore molecular sieves, AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK,CAS, CHA, CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU,PHI, RHO, ROG; THO, and substituted forms thereof; the medium poremolecular sieves, AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON, andsubstituted forms thereof; and the large pore molecular sieves, EMT,FAU, and substituted forms thereof. Other molecular sieves include ANA,BEA, CFI, CLO, DON, GIS, LTL, MER, MOR, MWW, and SOD. Non-limitingexamples of the preferred molecular sieves, particularly for convertingan oxygenate containing feedstock into olefin(s), include AEL, AFY, BEA,CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM, andTON. In one preferred embodiment, the molecular sieve of the inventionhas an AEI topology or a CHA topology, or a combination thereof, mostpreferably a CHA topology.

Metalloaluminophosphate molecular sieves are particularly preferredmolecular sieves used in the manufacturing process of this invention. Inone embodiment, these particles are represented by the empiricalformula, on an anhydrous basis:mR:(M_(x)Al_(y)P_(z))O₂wherein R represents at least one templating agent, preferably anorganic templating agent; m is the number of moles of R per mole of(M_(x)Al_(y)P_(z))O₂ and m has a value from 0 to 1, preferably 0 to 0.5,and most preferably from 0 to 0.3; x, y, and z represent the molefraction of Al, P and M as tetrahedral oxides, where M is a metalselected from one of Group IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIB,and Lanthanide's of the Periodic Table of Elements, preferably M isselected from one of the group consisting of Si, Ge, Co, Cr, Cu, Fe, Ga,Ge, Mg, Mn, Ni, Sn, Ti, Zn, Zr, and mixtures thereof. In a particularembodiment, m is greater than or equal to 0.2, and x, y and z aregreater than or equal to 0.01. In another embodiment, m is greater than0.1 to about 1, x is greater than 0 to about 0.25, y is in the range offrom 0.4 to 0.5, and z is in the range of from 0.25 to 0.5, morepreferably m is from 0.15 to 0.7, x is from 0.01 to 0.2, y is from 0.4to 0.5, and z is from 0.3 to 0.5.

Other examples of metalloaluminophosphate molecular sieves useful in theprocess of this invention include those described in EP-0 888 187 B1(microporous crystalline metallophosphates, SAPO₄ (UIO-6)), U.S. Pat.No. 6,004,898 (molecular sieve and an alkaline earth metal), PCT WO01/62382 published Aug. 30, 2001 (integrated hydrocarbon co-catalyst),PCT WO 01/64340 published Sep. 7, 2001(thorium containing molecularsieve), and R. Szostak, Handbook of Molecular Sieves, Van NostrandReinhold, New York, N.Y. (1992), which are all herein fully incorporatedby reference.

Most preferably, the metalloaluminophosphate molecular sieve crystalspresent in the molecular sieve catalyst composition are selected fromthe group consisting of silicoaluminophosphate (SAPO) molecular sieves,aluminophosphate molecular sieves, and metal substituted forms thereof.Non-limiting examples of SAPO and AlPO molecular sieves that may bepresent in the molecular sieve catalyst of the invention includemolecular sieves selected from the group consisting of SAPO-5, SAPO-8,SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35,SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56,AlPO-5, AlPO-11, AlPO-1 8, AlPO-3 1, AlPO-34, AlPO-36, AlPO-37, AlPO-46,metal containing molecular sieves thereof, and mixtures thereof. Themore preferred molecular sieves include molecular sieves selected fromthe group consisting of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56,AlPO-18 AlPO-34, metal containing molecular sieves thereof, and mixturesthereof; even more preferably molecular sieves selected from the groupconsisting of SAPO-18, SAPO-34, AlPO-34, AlPO-18, metal containingmolecular sieves thereof, and mixtures thereof; and most preferablymolecular sieves selected from the group consisting of SAPO-34, AlPO-18,metal containing molecular sieves thereof, and mixtures thereof.

As used herein, the term mixture is synonymous with combination and isconsidered a composition of matter having two or more components invarying proportions, regardless of their physical state. With regard tothe molecular sieve crystal components of the catalyst, the term furtherencompasses physical mixtures of crystalline and amorphous components,as well as intergrowths of at least two different molecular sievestructures, such as, for example those described in PCT Publication No.WO 98/15496.

In one embodiment, the molecular sieve crystal is an intergrowthmaterial having two or more distinct phases of crystalline structureswithin one molecular sieve composition. In another embodiment, themolecular sieve crystal comprises at least one intergrown phase of AEIand CHA framework-types. For example, SAPO-18, AlPO-18 and RUW-18 havean AEI framework-type, and SAPO-34 has a CHA framework-type. In afurther embodiment, the molecular sieve crystal comprises a mixture ofintergrown material and non-intergrown material.

C. Clay Component

The clay component of the catalyst of this invention can be a natural orsynthetic clay. Naturally occurring clays or modified natural occurringclays, e.g., partially dried or dehydrated, milled or micronized, orchemically treated are preferred. Such naturally occurring clays includeclays from the kaolinite group, the mica group, the smectite group, andthe chlorite group. Examples of kaolinite group clays include kaolinite,dickite and halloysite. Examples of the mica group clays includemuscovite, illite, glauconite and biotite. Examples of the smectitegroup include montmorillonite and vermiculite. Examples of the chloritegroup include penninite, clinochlore, ripidolite and chamosite.

Mixed layer clays can also be used. These clays are made of a regular orrandom stacking of layers composed of members of one or more groups ofclay minerals. Chlorite may be seen as a regular alternation of mica andbrucite layers. Random mixed layering of three layer clays is common,with examples being mixed layer mica/smectite and chlorite/vermiculite.In regular mixed layer structures such as chlorite, the basal spacing isa combination of that of the individual layers. In random mixed layeringthere is a non-integral series of reflections from the basal planes.This is shown as a composite reflection intermediate in position betweenthose of the individual layers, or as a spreading of the reflection.Thus, when a significant amount of smectite is interlayered with mica ina random manner, the mica peak will not be sharp, but will be spreadtoward the lower angle smectite reflection. The amount of spreadingdepends on the amount of mixed layering that exists.

D. Binder Component

Binders that are used in this invention are materials that act likeglue, binding together the molecular sieve crystals and other materials,to form a formulated molecular sieve catalyst composition. Non-limitingexamples of binders that can be used in this invention include varioustypes of inorganic oxide sols such as an inorganic oxide sol of aluminaor silica, and, in particular, aluminum chlorohydrate, hydratedaluminas, silicas, and/or other inorganic oxide sols.

E. Catalyst Composition Characteristics

One characteristic of the formulated catalyst composition of thisinvention is that it is highly attrition resistant, as measured by theAttrition Rate Index (ARI) method. The ARI is used over othermeasurement methods, since many other methods are not sufficient tomeasure very highly attrition resistant molecular sieve catalysts suchas those made according to this invention.

The ARI methodology is similar to the conventional Davison Index method.The smaller the ARI is, the more resistant to attrition the catalyst is.The ARI is measured by adding 6.0±0.1 g of catalyst having a particlessize ranging from 53 to 125 microns to a hardened steel attrition cup.Approximately 24,000 scc/min of nitrogen gas is bubbled through awater-containing bubbler to humidify the nitrogen. The wet nitrogenpasses through the attrition cup, and exits the attrition apparatusthrough a porous fiber thimble. The flowing nitrogen removes the finerparticles, with the larger particles being retained in the cup. Theporous fiber thimble separates the fine catalyst particles from thenitrogen that exits through the thimble. The fine particles remaining inthe thimble represent catalyst that has broken apart through attrition.

The nitrogen flow passing through the attrition cup is maintained for 1hour. The fines collected in the thimble are removed from the unit. Anew thimble is then installed. The catalyst left in the attrition unitis attrited for an additional 3 hours, under the same gas flow andmoisture levels. The fines collected in the thimble are recovered. Thecollection of fine catalyst particles separated by the thimble after thefirst hour are weighed. The amount in grams of fine particles divided bythe original amount of catalyst charged to the attrition cup expressedon per hour basis is the ARI, in wt %/hr.ARI=C/(B+C)/D×100%wherein

-   B=weight of catalyst left in the cup after the attrition test,-   C=weight of collected fine catalyst particles after the first hour    of attrition treatment, and-   D=duration of treatment in hours after the first hour attrition    treatment.

In one embodiment, the formulated catalyst composition has an attritionresistance index of not greater than 2 wt %/hr. Preferably, wherein thecatalyst composition has an attrition resistance index (ARI) of notgreater than 1.5 wt %/hr, and more preferably not greater than 1 wt%/hr.

The catalyst composition of the invention also has a relatively highdensity relative to conventional catalysts. In particular, the catalystcomposition of the invention has a relatively high apparent bulk density(ABD) relative to conventional catalysts.

According to the invention, one way of measuring ABD was using thefollowing procedure. A KIMAX graduated cylinder from KAMLE USA, accurateto 0.05 cc and having a 25 cc capacity, was used to weigh catalyst. Theempty cylinder was weighed and the weight recorded as W_(a).Approximately 25 cc of spray dried and calcined catalyst was poured intothe cylinder, and the cylinder was tapped against a lab bench surface ata frequency of 160-170 times per minute for 30 seconds to pack thecylinder into the cylinder. The weight of the packed cylinder wasweighed and recorded as W_(b). The volume of the catalyst in thecylinder was determined by reading the level of the packed catalyst inthe cylinder and recorded as V_(c). ABD was then calculated asABD=(W_(b)−W_(a))/V_(c).

In one embodiment, the catalyst composition has an apparent bulk density(ABD) of at least 0.78 g/cc. Preferably, the catalyst composition has anABD of at least 0.79 g/cc, more preferably at least 0.8 g/cc, and mostpreferably at least 0.81 g/cc. Generally, the catalyst density is notsignificantly greater than water. In one embodiment, the catalystcomposition has an ABD not greater than 1 g/cc. Preferably, the catalystcomposition has an ABD not greater than 0.99 g/cc, and more preferablynot greater than 0.98 g/cc.

The catalyst composition of this invention is a dried catalystcomposition. It can be dried so that it retains a template within thepore structure of the molecular sieve component, such as by spraydrying, or it can be further dried, such as by calcining, which removesthe template from the pore structure. Because the dried catalyst isattrition resistant, it is not necessary to calcine the formulatedcomposition prior to use. For example, the dried composition can beloaded into a reaction system so that conditions within the systemremove the template to activate the catalyst for use during operation ofthe reaction process.

IV. Making Formulated Molecular Sieve Catalyst

A. Components of Formulated Molecular Sieve Catalyst

Molecular sieve catalyst, which contains molecular sieve crystalproduct, binder and matrix materials, is also referred to as aformulated catalyst. It is made by mixing together molecular sievecrystals (which preferably includes template) and a liquid (preferablywater), with matrix material and binder, to form a slurry. The slurry isthen dried (i.e., liquid is removed). Preferably, the slurry is driedwithout completely removing the template from the molecular sieve, suchas by spray drying. Then, the spray dried catalyst is calcined to removeadditional water and the template material. Once template material isremoved, the catalyst is considered activated.

The liquid used to form the slurry can be any liquid conventionally usedin formulating molecular sieve catalysts. Non-limiting examples ofsuitable liquids include water, alcohol, ketones, aldehydes, esters, ora combination thereof. Water is a preferred liquid. The water can comefrom a variety of sources, including from process water of an oxygenateto olefins reaction process. In the oxygenate to olefins process, asubstantial amount of water is produced. With some clean-up, e.g.,removal of solids and hydrocarbon contaminants, the water can be re-usedin a variety of ways, including making the slurry solution. The watercan also be used in the direct manufacture of the molecular sieveitself.

Matrix materials are preferably included in the slurry. Such materialsare typically effective in the formulated molecular sieve catalystproduct as thermal sinks assisting in shielding heat from the catalystcomposition, for example, during regeneration. They can further act todensify the catalyst composition, increase catalyst strength such ascrush strength and attrition resistance, and to control the rate ofconversion in a particular process. Non-limiting examples of matrixmaterials include one or more of: rare earth metals, metal oxidesincluding titania, zirconia, magnesia, thoria, beryllia, quartz, silicaor sols, and mixtures thereof; for example, silica-magnesia,silica-zirconia, silica-titania, silica-alumina, andsilica-alumina-thoria.

One preferred type of matrix material used to make the catalyst of thisinvention is clay. Particularly preferred clays include kaolins such as,for example, Dixie, McNamee, Georgia, and Florida clays. Optionally, thematrix material, preferably any of the clays, are calcined, acidtreated, and/or chemical treated before being used as a slurrycomponent.

In a particular embodiment, the clay has a low iron or titania content,and is most preferably kaolin clay. Kaolin has been found to form apumpable, high solid content slurry; it has a low fresh surface area,and it packs together easily due to its platelet structure.

Preferably, the clay has an average particle size of from about 0.05 μmto about 0.75 μm; more preferably from about 0.1 μm to about 0.6 μm. Itis also desirable that the clay material have a d₉₀ particle sizedistribution of less than about 1.5 μm, preferably less than about 1 μm.

Binders are also included in the slurry used to make the formulatedmolecular sieve catalyst of this invention. In one embodiment of theinvention, the binder is an alumina-containing sol, preferably aluminiumchlorohydrate. Upon calcining, the inorganic oxide sol, is convertedinto an inorganic oxide matrix component, which is particularlyeffective in forming an attrition resistant molecular sieve catalystcomposition. For example, an alumina sol will convert to an aluminiumoxide matrix following heat treatment.

Aluminium chlorohydrate, a hydroxylated aluminium based sol containing achloride counter ion, also known as aluminium chlorohydrol, has thegeneral formulaAl_(m)O_(n)(OH)_(o)Cl_(p).x(H₂O)wherein m is 1 to 20, n is 1 to 8, o is 5 to 40, p is 2 to 15, and x is0 to 30. In one embodiment, the binder is Al₁₃O₄(OH)₂₄Cl₇.12(H₂O) as isdescribed in G. M. Wolterman, et al., Stud. Surf. Sci. and Catal., Vol.76, pp. 105-144, Elsevier, Amsterdam, 1993, which is herein incorporatedby reference. In another embodiment, one or more binders are present incombination with one or more other non-limiting examples of aluminamaterials such as aluminium oxyhydroxide, γ-alumina, boehmite andtransitional aluminas such as β-alumina, γ-alumina, δ-alumina,ε-alumina, κ-alumina, and ρ-alumina, aluminium trihydroxide, such asgibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.

Aluminum chlorohydrate can be prepared by dissolving either metallicaluminum or hydrated alumina in hydrochloric acid under controlledconditions, and is available commercially in different forms, such assolid products; for example, the solid of chemical formulaAl₂(OH)₅Cl.n(H₂O) or as pre-prepared, commercially available, aqueoussolutions. Other non-limiting examples of useful aluminum oxideprecursors that may be used according to this invention include aluminumhexahydrate, aluminum pentachlorohydrate (Al₂(OH)Cl₅), aluminumtetrachlorohydrate (Al₂(OH)₂Cl₄), aluminum trichlorohydrate(Al₂(OH)₃Cl₃), aluminum dichlorohydrate (Al₂(OH)₄Cl₂), aluminumsesquichlorohydrate (Al₂(OH)_(4.5)Cl_(1.5)).

Other non-limiting examples of binders useful according to thisinvention include precursors of aluminum-zirconium oxides. Suchprecursors include, but are not limited to, aluminum zirconiumchlorohydrates; for example, aluminum zirconium trichlorohydrate,aluminum zirconium tetrachlorohydrate, aluminum zirconiumpentachlorohydrate, aluminum zirconium octachlorohydrate, aluminumzirconium chlorhydrex, aluminum zirconium chlorhydrex glycine complexes(e.g., aluminum zirconium trichlorohydrex glycine complex, aluminumzirconium tetrachlorohydrex glycine complex, aluminum zirconiumpentachlorohydrex glycine complex, and aluminum zirconiumoctachlorohydrex glycine complex). In the absence of glycine, thesematerials form gels in aqueous solutions. Reheis Chemicals Inc.,Berkeley Heights, N.J. produces a variety of aluminum zirconiumchlorohydrates. These materials can be prepared from a variety ofzirconium starting materials such as zirconyl chloride (ZrOCl₂),zirconyl hydroxychloride (ZrO(OH)Cl), zirconium hydroxy carbonate paste(ZrO(OH)(CO₃)_(0.5)), and combinations of these zirconium startingmaterials, with a hydrated aluminum solution, such as a solution ofaluminum chlorohydrate, aluminum hexahydrate, aluminumsesquichlorohydrate or aluminum dichlorohydrate solution, or a solutionobtained by combining one or several of these aluminum speciessolutions.

In another embodiment, the binders are alumina sols, predominantlycomprising aluminium oxide, optionally, including silicon. In yetanother embodiment, the binders are peptised alumina made by treatingalumina hydrates such as pseudobohemite, with an acid, preferably anon-halogen acid, to prepare sols or aluminium ion solutions.Non-limiting examples of commercially available colloidal alumina solsinclude Nalco 8676 available from Nalco Chemical Co., Naperville, Ill.,and Nyacol available from the Nyacol Nano Technology Inc., Boston, Mass.

In a preferred embodiment, the amount of binder used to prepare themolecular sieve catalyst composition is at least 5 wt %, based on totalweight of the material used to make the composition, excluding liquid(i.e., after drying), particularly excluding water. Preferably theamount of binder used to prepare the molecular sieve catalyst is atleast 8 wt %, and more preferably at least 10 wt %, based on totalweight of the material used in making the catalyst, excluding liquid(i.e., after drying). It is also preferred that the amount of binderused to prepare the molecular sieve catalyst is not greater than about50 wt %, preferably not greater than 40 wt %, and more preferably notgreater than 30 wt %, based on total weight of the material used inmaking the catalyst, excluding liquid (i.e., after drying).

B. Making a Slurry with Molecular Sieve Crystals

The molecular sieve crystals are mixed with clay and binder, as well asliquid solvent component, to form a slurry. The components can be mixedin any order. In a particular embodiment, binder is added to a liquid,molecular sieve then added, followed by clay addition. The mixture isthoroughly stirred, preferably using a rotor-stator mixing unit havingappropriate characteristics to form the slurry. Examples of desiredcharacteristics are detailed above.

The molecular sieve crystals, clay, and binder are mixed together toform a slurry having a desired solids content. The solids content shouldbe sufficiently high, otherwise a less attrition resistant catalyst willbe formed.

In one embodiment, molecular sieve crystals, clay, and binder are mixedtogether to form a slurry having a solids content of at least 40 wt %,based on total weight of the slurry mixture. Preferably, molecular sievecrystals, clay, binder and water are mixed to form a slurry having asolids content of at least 41 wt %, more preferably at least 43 wt %,and most preferably at least 44 wt %, based on the total weight of theslurry.

The solids content can be measured using any conventional means.However, a CEM MAS 700 microwave muffle furnace (CEM Corp., Matthews,N.C.) is particularly preferred to give results consistent with thevalues recited herein. It is also preferred that the slurry have asolids content of not greater than 60 wt %, based on total weight of theslurry. Preferably, the slurry has a solids content of not greater than58 wt %, more preferably not greater than 56 wt %, and most preferablynot greater than 54 wt % based on total weight of the slurry.

In another embodiment of the invention, the molecular sieve crystals,clay, and binder are mixed together to form a slurry mixture at a binderto molecular sieve weight ratio of at least 0.20:1. Preferably, themolecular sieve crystals, clay, and binder are mixed together at abinder to molecular sieve weight ratio of at least 0.22:1, morepreferably at least 0.24:1, and most preferably at least 0.25:1. It isalso preferred that the crystals, clay, and binder be mixed together ata binder to molecular sieve weight ratio of not greater than 0.8:1,preferably not greater than 0.6:1.

In another embodiment, the molecular sieve crystals, clay, and binderare mixed together to form a slurry mixture at a binder content of atleast 5 wt %, preferably at least 8 wt %, and more preferably at least10 wt %, based on total weight of the mixture, excluding liquid (e.g.,water). It is also preferred in an embodiment that the molecular sievecrystals, clay, and binder are mixed together to form a slurry mixtureat a binder content of not greater than 30 wt %, preferably not greaterthan 25 wt %, based on total weight of the mixture, excluding liquid(e.g., water).

The temperature at which the slurry is made can range. Examples of suchconditions include temperatures ranging from 0° C. to 100° C.,preferably of from 10° C. to 90° C., more preferably of from 15° C. to80° C., most preferably of from 20° C. to 70° C.

In-tank or batch operation can be operated for some duration to ensureproper mixing and viscosity. In one embodiment, the rotor-stator mixeris in-tank operated for a period of at least 2 hours, preferably atleast 4 hours, more preferably at least 5 hours, and most preferably atleast 6 hours. In a preferred embodiment, mixing of slurry components isperformed for not more than 150 hours, preferably not more than 120hours, most preferably not more than 100 hours. Other preferred batchmixing conditions include mixing at a temperature of from 30° C. to 50°C. for a period of from 4 hours to 80 hours, preferably from 5 hours to75 hours, more preferably of from 5.5 hours to 50 hours, most preferablyof from 6 hours to 36 hours.

C. Drying the Slurry

In one embodiment, the slurry of the molecular sieve, binder, and matrixmaterials is fed to a forming unit that produces a dried molecular sievecatalyst composition. Non-limiting examples of forming units includespray dryers, pelletizers, extruders, etc. In a preferred embodiment,the forming unit is spray dryer. Typically, the forming unit ismaintained at a temperature sufficient to remove most of the liquid(e.g., water) from the slurry.

When a spray dryer is used as the forming (or drying) unit, typically,the slurry of the molecular sieve, matrix material and binder, is co-fedto the drying unit with a drying gas. In one embodiment the drying unithas an average inlet temperature ranging from 150° C. to 550° C., and anaverage outlet temperature ranging from 100° C. to about 250° C.

In one embodiment, the slurry is passed through a nozzle distributingthe slurry into small droplets, resembling an aerosol spray, into adrying chamber. Atomization is achieved by forcing the slurry through asingle nozzle or multiple nozzles with a pressure drop in the range offrom 100 psia to 1000 psia (690 kPaa to 6895 kPaa). In anotherembodiment, the slurry is co-fed through a single nozzle or multiplenozzles along with an atomization fluid such as air, steam, flue gas, orany other suitable gas.

In yet another embodiment, the slurry described above is directed to theperimeter of a spinning wheel that distributes the slurry into smalldroplets, the size of which is controlled by many factors includingslurry viscosity, surface tension, flow rate, pressure, and temperatureof the slurry, the shape and dimension of the nozzle(s), or the spinningrate of the wheel. These droplets are then dried in a co-current orcounter-current flow of air passing through a spray drier to form apartially, substantially or totally dried molecular sieve catalystcomposition.

In another embodiment of the invention, the slurry is dried in a dryingunit and then calcined. In one embodiment, the slurry is dried to form adried molecular sieve catalyst composition, and the dried catalystcomposition is calcined. In general, calcination further hardens and/oractivates the dried molecular sieve catalyst composition. An acceptablecalcination environment is air that typically includes a small amount ofwater vapour. Typical calcination temperatures are in the range fromabout 400° C. to about 1,000° C., preferably from about 500° C. to about800° C., and most preferably from about 550° C. to about 700° C.,preferably in a calcination environment such as air, nitrogen, helium,flue gas (combustion product lean in oxygen), steam, or any combinationthereof.

The dried or formulated molecular sieve catalyst composition can becalcined in many types of devices, including but not limited to, rotarycalciners, fluid bed calciners, batch ovens, and the like. Calcinationtime is typically dependent on the degree of hardening of the molecularsieve catalyst composition and the temperature.

In a preferred embodiment, the molecular sieve catalyst composition isheated in nitrogen at a temperature of from about 600° C. to about 700°C. Heating is carried out for a period of time typically from 1 minuteto 15 hours, preferably from 2 minutes to about 10 hours, morepreferably from about 3 minutes to about 5 hours, and most preferablyfrom about 5 minutes to about 4 hours.

V. Methods of using Catalyst

The molecular sieve catalyst product made according to this invention isuseful in a variety of processes including cracking of, for example, anaphtha feed to light olefin(s) (U.S. Pat. No. 6,300,537) or highermolecular weight (MW) hydrocarbons to lower MW hydrocarbons;hydrocracking of, for example, heavy petroleum and/or cyclic feedstock;isomerization of, for example, aromatics such as xylene; polymerizationof, for example, one or more olefin(s) to produce a polymer product;reforming; hydrogenation; dehydrogenation; dewaxing of, for example,hydrocarbons to remove straight chain paraffins; absorption of, forexample, alkyl aromatic compounds for separating out isomers thereof;alkylation of, for example, aromatic hydrocarbons such as benzene andalkyl benzene, optionally with propylene to produce cumene or with longchain olefins; transalkylation of, for example, a combination ofaromatic and polyalkylaromatic hydrocarbons; dealkylation;hydrodecyclization; disproportionation of, for example, toluene to makebenzene and paraxylene; oligomerization of, for example, straight andbranched chain olefin(s); and dehydrocyclization.

Preferred processes include processes for converting naphtha to highlyaromatic mixtures; converting light olefin(s) to gasoline, distillatesand lubricants; converting oxygenates to olefin(s); converting lightparaffins to olefins and/or aromatics; and converting unsaturatedhydrocarbons (ethylene and/or acetylene) to aldehydes for conversioninto alcohols, acids, and esters.

The most preferred process of the invention is a process directed to theconversion of a feedstock to one or more olefin(s). Typically, thefeedstock contains one or more aliphatic-containing compounds such thatthe aliphatic moiety contains from 1 to about 50 carbon atoms, such asfrom 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms, andparticularly from 1 to 4 carbon atoms. Non-limiting examples ofaliphatic-containing compounds include alcohols such as methanol andethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan,alkyl sulfides such as methyl sulfide, alkylamines such as methylamine,alkyl ethers such as dimethyl ether, diethyl ether and methylethylether, alkyl halides such as methyl chloride and ethyl chloride, alkylketones such as dimethyl ketone, formaldehydes, and various acids suchas acetic acid.

The catalyst made according to the process of this invention has anattrition resistance that is suitable for use in a wide variety ofreaction processes. Examples of such processes include a fixed-bedprocess, or more typically as a fluidized-bed process (including aturbulent-bed process), such as a continuous fluidized-bed process, andparticularly a continuous high-velocity, fluidized-bed process.

VI. Examples of Methods of Making Slurry and Catalyst

EXAMPLES 1-6

Examples 1-6 show the rheological behavior of a catalyst formulationusing an intergrown AEI/CHA molecular sieve, wherein slurry viscositydecreases as function of milling (number of passes). The components ofthe formulation are mixed using a Silverson L4RT-A in-line mixer (rotorsize: 1.25″, Silverson Machines, Inc., East Longmeadow, Mass.) at6000-7500 RPM using a square hole screen (gap size: 3/1000″). Theviscosity results of a 44.87-45.41% solids content slurry containing 45%molecular sieve, 13.5% aluminum chlorohydrate (ACH, Reheis, Inc.,Berkeley Heights, N.J.) and 41.5% kaolin clay (ASP Ultrafine, EngelhardCorp., Rosewell, Ga.), based on total weight of the slurry excludingliquid, are given in Table 1. TABLE 1 Milling and Slurry ConditionsProduct and Slurry Properties Solids Micropore Ex. Number ContentMilling ABD ARI Surface Area Viscosity No. of Passes wt % (RPM) (g/cc)(wt %/hr) (m²/g) (cP; @ 10 RPM) 1 0 45.04 6000 0.77 2.41 231 10700 2 344.89 6000 0.79 2.02 230.9 9500 3 15 45.41 6000 0.78 1.59 228.8 7400 430 45.05 7500 0.83 0.78 231.8 6400 5 60 44.87 7500 0.83 0.42 223.7 32006 100 45.25 7500 0.83 0.47 232 2900

EXAMPLE 7

This example shows the rheological behavior of a catalyst formulationusing an intergrown AEI/CHA molecular sieve, wherein slurry viscosityincreases as function of milling (number of passes). The components ofthe formulation are mixed using a Silverson 150L in-line mixer (rotorsize: 1.5″) at 5000 RPM using a round hole screen (gap size: 7/1000″).The viscosity results of a 42.3% solids content slurry containing 45%molecular sieve, 13.5% aluminum chlorohydrate (ACH) and 41.5% kaolinclay, based on total weight of the slurry excluding liquid, are given inTable 2. TABLE 2 Number of Viscosity Passes (cP; @ 10 RPM) 2.5 4256 104544 25 4487 55 5243

EXAMPLE 8

This example shows the rheological behavior of a catalyst formulationusing an intergrown AEI/CHA molecular sieve, wherein slurry viscosityincreases as function of milling (number of passes). The components ofthe formulation are mixed using a Silverson 150L in-line mixer (rotorsize: 1.5″) at 5000 RPM using a round hole screen (gap size: 7/1000″).The viscosity results of a 43.7% solids content slurry containing 45%molecular sieve, 13.5% aluminum chlorohydrate (ACH) and 41.5% kaolinclay, based on total weight of the slurry excluding liquid, are given inTable 3. TABLE 3 Viscosity Number of Passes (cPs; @ 10 RPM) 2.5 7019 258253 85 8952 105 9175

EXAMPLE 9

This example shows the rheological behavior of a catalyst formulationusing an intergrown AEI/CHA molecular sieve, wherein slurry viscositydecreases as function of milling (number of passes). The components ofthe formulation are mixed using a Silverson 150L in-line mixer (rotorsize: 1.5″) at 5000 RPM using a square hole screen (gap size: 3/1000″).The viscosity results of a 41.2% solid content slurry containing 45%molecular sieve, 13.5% aluminum chlorohydrate (ACH) and 41.5% kaolinclay, based on total weight of liquid, are given in Table 4. TABLE 4Viscosity Number of Passes Solids Content (wt. %) (cP; @ 10 RPM) 0 41.215513 1 41.2 13558 12 41.2 11803 27 41.2 9881 40 41.2 8648 65 41.2 6921

The data in the tables indicate that, in general, slurry viscosityincreases as milling increases when only round hole stators are used.Slurries having very high viscosities are not as desirable, becauseslurries with relatively high viscosities are difficult to process(e.g., hard to pump). In addition, high viscosity slurries will tend toproduce dried catalyst particles that are more susceptible to attrition,i.e., have higher attrition rate indices (ARIs).

The principles and modes of operation of this invention have beendescribed above with reference to various exemplary and preferredembodiments. As understood by those of skill in the art, the overallinvention, as defined by the claims, encompasses other preferredembodiments not specifically enumerated herein.

1. A method of making an attrition resistant molecular sieve catalystcomposition, comprising the steps of: a) mixing together molecular sievecrystals, clay, binder, and liquid with a rotor-stator mixer to form aslurry having a solids content of at least 40 wt %, based on totalweight of the slurry; b) progressing the mixing until slurry viscositydecreases; and c) drying the slurry to produce a dried molecular sievecatalyst composition having an attrition rate index of not greater than2 wt %/hr.
 2. The method of claim 1, wherein the slurry is mixed untilthe viscosity is decreased by at least about 10%.
 3. The method of claim2, wherein the slurry is mixed until the viscosity is decreased by atleast 15%.
 4. The method of claim 3, wherein the slurry is mixed untilthe viscosity is decreased by at least 20%.
 5. The method of claim 1,wherein the stator has at least one polygonal shaped hole defining anopening of not greater than 9 mm².
 6. The method of claim 5, wherein theat least one polygonal shaped hole has at least one angle not greaterthan 90 degrees.
 7. The method of claim 6, wherein the at least onepolygonal shaped hole is a rectangle.
 8. The method of claim 7, whereinthe at least one polygonal shaped hole is a square.
 9. The method ofclaim 5, wherein the rotor and stator have a gap distance of not greaterthan 0.3 mm.
 10. The method of claim 9, wherein the rotor and statorhave a gap distance of not greater than 0.28 mm.
 11. The method of claim5, wherein each hole defines an opening of not greater than 7.5 mm². 12.The method of claim 5, wherein the stator has at least 4 holes persquare inch of surface area.
 13. The method of claim 1, wherein themolecular sieve crystals, clay, binder, and liquid are mixed with anin-line rotor-stator mixer applying recycle at a number of passes of atleast
 1. 14. The method of claim 1, wherein the rotor is rotated at atip speed of at least 5 m/sec.
 15. The method of claim 1, wherein theslurry is dried by a combination of spray drying and calcining.
 16. Themethod of claim 1, wherein the molecular sieve crystals, clay, binder,and liquid are mixed to form a slurry having a viscosity of not greaterthan 10,000 cP.
 17. The method of claim 1, wherein the clay is a naturalor synthetic clay.
 18. The method of claim 1, wherein the binder is aninorganic oxide sol of alumina or silica.
 19. The method of claim 1,wherein the molecular sieve crystals, clay, binder, and liquid are mixedtogether to form a slurry having a viscosity of at least 500 cP.
 20. Themethod of claim 1, wherein the molecular sieve crystals, clay, binder,and liquid are mixed together to form a slurry having a solids contentof not greater than 60 wt %, based on total weight of the slurry. 21.The method of claim 1, wherein the molecular sieve particles aremetalloaluminophosphate molecular sieve crystals.
 22. The method ofclaim 21, wherein the metalloaluminophosphate molecular sieve crystalsare selected from the group consisting of SAPO-5, SAPO-8, SAPO-11,SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36,SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, AlPO-5,AlPO-11, AlPO-18, AlPO-31, AlPO-34, AlPO-36, AlPO-37, AlPO-46, metalcontaining molecular sieves thereof, and mixtures thereof.
 23. Themethod of claim 22, wherein the dried metalloaluminophosphate molecularsieve catalyst is contacted with oxygenate to form olefin product.
 24. Aprocess for making olefin product, comprising the steps of: a) mixingtogether metalloaluminophosphate molecular sieve crystals, clay, binder,and liquid with a rotor-stator mixer to form a slurry having a solidscontent of at least 40 wt %, based on total weight of the slurry, and aviscosity of not greater than 10,000 cP, wherein the rotor and statorhave a gap distance of not greater than 0.3 mm and the stator has aplurality of polygonal shaped holes, each hole defining an opening ofnot greater than 9 mm²; b) drying the slurry to produce a driedmolecular sieve catalyst composition having an attrition rate index ofnot greater than 2 wt %/hr; c) contacting the driedmetalloaluminophosphate molecular sieve catalyst with oxygenate to formolefin product.
 25. The method of claim 24, wherein the at least onepolygonal shaped hole has at least one angle not greater than 90degrees.
 26. The method of claim 25, wherein the at least one polygonalshaped hole is a rectangle.
 27. The method of claim 26, wherein the atleast one polygonal shaped hole is a square.
 28. The method of claim 24,wherein the rotor and stator have a gap distance of not greater than0.28 mm.
 29. The method of claim 24, wherein each hole defines anopening of not greater than 7.5 mm₂.
 30. The method of claim 24, whereinthe stator has at least 4 holes per square inch of surface area.